ApplicationNo. 10681671 filed on 10/07/2003
US Classes:95/134, Mercury sorbed 95/900, SOLID SORBENT 96/108, SOLID SORBENT APPARATUS 210/688, Heavy metal 423/210, MODIFYING OR REMOVING COMPONENT OF NORMALLY GASEOUS MIXTURE 285/39, Particular tool-engaging means or with tool 423/562, Polysulfide 117/62, Electric current controlled or induced growth 428/419, Of polythioether 536/107, Esters 208/251H, Employing hydrogen 423/243.1, And additional ionic reactant 210/218, Gas removed from closed tank 433/92, And suction pump or material separator 209/166, With modifying agents 423/42, Forming insoluble substance in liquid 210/721, Including oxidation 427/361, Paper base (e.g., calendering, etc.) 210/712, Including recycling 210/670, Including rehabilitating or regenerating exchange material or sorbent 502/338, Of iron 502/216, Sulfur or compound containing same 210/265, With gravitational separator 210/718, Including degassing 210/679, Utilizing exchange or sorbent material associated with inert material 502/403, Protein 210/728, Including organic agent 423/659, MISCELLANEOUS PROCESS 585/820, By contact with solid sorbent 252/189, CO, S, NEGATIVE ELEMENT, OR ACID, BINDANT CONTAINING 210/719, Including chemical reduction 494/43, ROTATABLE BOWL 134/2, For metallic, siliceous, or calcareous basework, including chemical bleaching, oxidation or reduction 502/414, Aluminum containing 210/665, By making an insoluble substance or accreting suspended constituents 521/28, Previously formed solid ion-exchange polymer admixed with nonreactive material or ion-exchange polymer 210/715, Utilizing sludge or floc blanket 208/251R, Metal contaminant removal 208/253, With metal or metal compound 210/674, Utilizing organic regenerant 423/4, Removing cladding or coating from fuel element 210/788, Introducing liquid tangentially 210/660, Ion exchange or selective sorption 585/867, Hydrocarbon 210/263, PARTICULATE MATERIAL TYPE SEPARATOR, E.G., ION EXCHANGE OR SAND BED 502/516, Metal contaminant removal 95/123, Hot sweep gas 95/141, Organic gas or liquid particle sorbed (e.g., vapor, mist, etc.) 75/388, Preparing for amalgamation, preparing and amalgamating, or breaking amalgam to produce free metal 423/245.1, Organic component 210/661, By passing through suspended bed 585/823, Sorbate is nonhydrocarbon or chemically undetermined component, e.g., "color-former", etc. 210/256, One unit inside another 210/664, By distilling or degassing 423/566.1, Sulfide of Cd, Zn, or Hg 502/417, And specified adde active sorbent material 423/235, Nitrogen or nitrogenous component 210/143, AUTOMATIC CONTROL 75/742, Cleaning, leaching, or dissolving of Mercury(Hg) 423/101, Forming insoluble substance in liquid 210/713, Of separated solids 585/648, By C content reduction, e.g., cracking, etc. 210/716, Including step of manufacturing inorganic treating agent 210/673, Utilizing gas, water, or chemical oxidizing or reducing agent 210/717, In situ 524/30, Atom other than N, O, H, C, S, or Group IA metal 502/415, Alumina (i.e., dialuminum trioxide) 525/332.2, Divinyl benzene 427/212, PARTICLES, FLAKES, OR GRANULES COATED OR ENCAPSULATED 502/84, And metal, metal oxide, or metal hydroxide 588/18, Chemical conversion to a stable solid for disposal 75/724, Displacing by another metal (i.e., electromotive series) 75/670, Mercury(Hg) 210/669, Prior to ion exchange or sorption 210/651, Removing specified material 423/99, Group IIB metal (Zn, Cd, or Hg) 210/723, Utilizing precipitant, flocculant, or coagulant, each with accelerator or with each other or plural precipitants, flocculants, or coagulants 422/170, Plural chemical reaction stages 422/169, Including means providing sequential purification stages 252/180, Plant or organic material containing 210/681, Removing ions 422/172, And means downstream of a stage for injecting a reactant into waste gas for interreaction in subsequent stage 159/25.2, Vertical axis agitator 210/710, Treating the insoluble substance 95/58, With addition of solid, gas, or vapor 210/724, Regulating pH 502/411, Having extraneously added alkali metal, or alkaline earth metal 536/59, Sulfur containing acid 422/1, PROCESS DISINFECTING, PRESERVING, DEODORIZING, OR STERILIZING 588/256, Waste contains heavy metal (e.g., fly, ash, flue dust, and incinerator ash) 134/28, One an acid or an acid salt 210/711, For recovery of a treating agent 220/269, Gripping means attached to or integral with member or portion (e.g., pull tab) 96/157, With liquid level sensing means 423/576.8, By reacting gaseous feed with gas containing free oxygen 210/722, Of iron or manganese material 210/666, Utilizing organic agent 95/107, Moving sorbent 422/171, Solid, extended surface, fluid contact type 92/134, Fluid spring 423/245.3, By burning or catalytically combusting component 210/702, Making an insoluble substance or accreting suspended constituents 210/188, WITH GAS SEPARATOR 422/224, Including internal mixing or stirring means 95/133 Metal or metal containing compound sorbed
ExaminersPrimary: Spitzer, Robert
Attorney, Agent or Firm
Foreign Patent References
International ClassesB01D 53/04
FIELD OF THE INVENTION
The present invention is directed generally to mercury removal from fluids and specifically to mercury removal using ion-exchanged agents.
BACKGROUND OF THE INVENTION
In December, 2000, the U.S. Environmental Protection Agency (EPA) announced its intention to regulate mercury and other air toxic emissions from coal- and oil-fired power plants with implementation as early as November, 2007 (Johnson, J., "PowerPlants to Limit Mercury," Chemical and Engineering News, 2001, p. 18,79). The pending regulation has created an impetus in the utility industry to find cost-effective solutions to meet the impending mercury emission standards.
Mercury and its compounds are a group of chemicals identified in Title III of the 1990 Clean Air Act (CAA) Amendments as air toxic pollutants. Mercury is of significant environmental concern because of its toxicity, persistence in theenvironment, and bio-accumulation in the food chain. Mercury is one of the most volatile species of the 189 toxic compounds listed in the Clean Air Act Amendments and is, therefore, released readily into the environment from natural and anthropogenicsources. Because of its physical and chemical properties, mercury can also be transported regionally through various environmental cycles (Mercury Study Report to Congress, "Volume VIII: An Evaluation of Mercury Control Technologies and Costs," U.S. Environmental Protection Agency, EPA-452/R-97; 0.010, December, 1997). Atmospheric deposition of mercury is reported to be the primary cause of elevated mercury levels in fish found in water bodies remote from known sources of this heavy metal.
Domestic coal-fired power plants emit a total of about fifty metric tons of mercury into the atmosphere annually--approximately thirty-three percent of all mercury emissions (Mercury Study Report to Congress, "Volume I: Executive Summary," UnitedStates Environmental Protection Agency, EPA-452/R-97-010, December, 1997; Midwest Research Institute, "Locating and Estimating Air Emissions from Sources of Mercury and Mercury Compounds," EPA-45/R-93-023, September, 1993). Specially designedemission-control systems maybe required to capture these volatile compounds effectively. A coal-fired utility boiler emits several different mercury compounds, primarily elemental mercury and speciated mercury, such as mercuric chloride (HgCl2) andmercuric oxide (HgO)--each in different proportions, depending on the characteristics of the fuel being burned and on the method of combustion. Quantifying the rate and composition of mercury emitted from stationary sources has been the subject of muchrecent work (e.g., Devito, M. S. et al., "Flue Gas Hg Measurements from Coal-Fired Boilers Equipped with Wet Scrubbers," 92nd Annual Meeting Air & Waste Management Association, St. Louis, Mo., Jun. 21-24, 1999; Laudal, D. L. et al., "Bench and PilotScale Evaluation of Mercury Measurement Methods," DOE/EPRI/EPA Joint Workshop on Mercury Measurement and Speciation Methods, Research Triangle Park, NC, Jan. 29 30, 1997; Hargrove, O. W. et al., "Enhanced Control of Mercury by Wet FGD," proceedings ofFirst Joint Power and Fuel Systems Contractors Conference, Pittsburgh, P A, Jul. 9 11, 1996; Agbede, R. O., A. J. Bochan, J. L. Clements, R. P. Khosah, T. J. McManus, "A Comparative Evaluation of EPA Method 29, the Ontario Hydro Method, and New ImpingerSolution Methods for the Capture and Analysis of Mercury Species," proceedings of the First Joint Power and Fuel Systems Contractors Conference, Pittsburgh, Pa., Jul. 9 11, 1996). Mercury is found predominantly in the vapor-phase in coal-fired boilerflue gas (Mercury Study Report to Congress, "Volume VIII: An Evaluation of Mercury Control Technologies and Costs," United States Environmental Protection Agency, EPA-452/R-97-010, December, 1997). Mercury can also be bound to fly ash in the flue gas.
Today, only municipal solid waste (MSW) incinerators and medical waste combustors are regulated with respect to mercury emissions, and, until the present, the best available control technology for these incinerators is the injection of activatedcarbon. Although fairly effective for MSW incinerators, activated carbon is a less appealing solution for coal-fired flue gas streams because of the dramatic difference in mercury concentrations. Regulations for mercury control from municipal andmedical waste incinerators specify eighty percent control, or outlet emission levels of fifty micrograms per cubic meter (μg/m3). In coal-fired flue gas streams, typical uncontrolled mercury concentrations are on the order of 10 μg/m3. For such low concentrations, projected injection rates for activated carbon to maintain ninety percent control of mercury emissions from coal-fired flue gas streams are high--up to 10,000 pounds or more of activated carbon to remove one pound of mercury,depending on the concentration and speciation of mercury in the flue-gas. The mercury-contaminated carbon becomes part of the ash collected by particulate-control devices and can convert the fly ash from an asset to a liability.
At present, the injection of activated carbon is broadly considered the best available control technology for reduction of mercury emissions from coal-fired power plants that do not have wet scrubbers (about seventy-five percent of all plants). Tests of carbon injection, both activated and chemically impregnated, have been reported by several research teams: Miller, S. J., et al., "Laboratory-Scale Investigation of Sorbents for Mercury Control," paper number 94-RAI14A.O1, presented at the 87thAnnual Air and Waste Management Meeting, Cincinnati, Ohio, Jun. 19 24, 1994; Sjostrom, S., J. et al., "Demonstration of Dry Carbon-Based Sorbent Injection for Mercury Control in Utility ESPs and Baghouses," paper 97-W A 72A.O7, 90th Annual Meeting ofthe Air and Waste Management Association, Toronto, Ontario, Canada, Jun. 8 13, 1997; Bustard, C. J. et al., "Sorbent Injection for Flue-gas Mercury Control," presented at the 87th Annual Air and Waste Management Meeting, Cincinnati, Ohio, Jun. 19 24,1994; and Butz, J. R. et al., "Use of sorbents for Air Toxics Control in a Pilot-Scale COHP AC Baghouse," 92nd Annual Meeting Air & Waste Management Association, St. Louis, Mo., Jun. 21 24, 1999. Activated carbon injection ratios for effective mercurycontrol are widely variable and are explained by the dependence of the sorption process on flue gas temperature and mercury speciation and also on fly ash chemistry.
The effectiveness of carbon injection for mercury control is limited by sorbent capacity and flue-gas interactions with the activated carbon. Studies reported by Miller, S. J. et al., in "Mercury Sorbent Development for Coal-Fired Boilers,"presented at Conference on Air Quality: Mercury, Trace Elements, and Particulate Matter, McLean, Virginia, December 1998, at the University of North Dakota's Energy & Environmental Research Center (EERC) examined the effects of various acid gasconstituents on the sorption capacity of carbon in a full-factorial test matrix. The EERC workers fed elemental mercury through carbon samples and systematically changed the gas composition. They noted a limited impact by SO2, but a dramatic dropin capacity when HC1 or NO2 were present with SO2. Similar results were obtained in studies in a mercury test fixture by one of the applicants (Turchi, C., "Novel Process for Removal and Recovery of Vapor-Phase Mercury," Final Report for PhaseII, DOE Contract DE-AC22-95 PC95257, Sep. 29, 2000).
The cost to implement activated carbon mercury control systems has been estimated by the Department of Energy (DOE), EPA, and several researchers. Chang, R. et al., in "Mercury Emission Control Technologies," Power Engineering, November, 1995,pp. 51 56, state that with operating and amortized capital costs, carbon injection will cost between $14,000 and $38,000 per pound of mercury removed, which equates to over $4 million per year for a 250-megawatt (MW) power plant.
EPA estimated similar costs for a 975-MW power plant (Mercury Study Report to Congress, "Volume VIII: An Evaluation of Mercury Control Technologies and Costs," U.S. Environmental Protection Agency, EPA-452/R-97-010, December, 1997). In theirmodel, four mercury control scenarios were considered to achieve ninety percent reduction in mercury emissions for a plant with an existing ESP. The scenarios were: (1) activated carbon injection; (2) spray cooling and activated carbon injection; (3)spray cooling, activated carbon injection with added fabric filter collection device; and (4) added activated carbon filter bed. The most economical control option employed spray cooling with carbon injection, resulting in a specific cost of $14,000 perpound mercury removed.
The development of more efficient sorbents would greatly reduce the cost of this mercury control approach by decreasing the amount of sorbent injected, downsizing sorbent injection equipment, and reducing costs for handling and disposing of spentsorbent.
The potential limitations of carbon-based sorbents have led to research into other possible mercury sorbents. Research has demonstrated that noble-metal-impregnated alumina will remove elemental mercury and mercuric chloride from air streams. The sorbent can be thermally regenerated and the desorbed mercury captured in a condenser or oxidizing wet scrubber. Initial cost estimates looked attractive compared with the cost of disposable carbon sorbents (Turchi et al., "Removal of Mercury fromCoal Combustion Flue-Gas Using Regenerable Sorbents," 92nd Annual Meeting Air & Waste Management Association, St. Louis, Mo., Jun. 21 24, 1999). In 1998 and 1999, work at coal-combustion facilities in Pennsylvania and New Jersey demonstrated that thesorbent can function in flue-gas but at lower efficiency than was seen in the earlier laboratory tests. Subsequent lab work has suggested that acid-gas attack on the sorbent will reduce its effectiveness. There is also some indication of flue-gasinteractions similar to those witnessed by the EERC group. Research is continuing to determine whether the detrimental effects are temporary or permanent. Fixed beds of zeolites and carbons have been proposed for a variety of mercury-controlapplications, but none has been developed specifically for control of mercury in coal flue-gas. Products in this class include Lurgi GmbH's (Frankfurt, Germany) Medisorbon and Calgon Carbon Corporation's (Pittsburgh, Pa.) HGR. Medisorbon is asulfur-impregnated zeolite and costs -$17/lb. As with most sulfur-impregnated materials, Medisorbon loses sulfur when heated above 2000 F, due to the vapor pressure of sulfur.
Examples of other mercury sorbents are discussed in Sugier et al. in U.S. Pat. No. 4,094,777. Sugier et al. discloses a process for removing mercury from a gas or liquid. This invention is limited in that it requires impregnation of a supportonly with copper and silver, although other metals can be present, for example iron. Moreover, the supports taught by the reference are limited to silica; alumina, silica-alumina, silicates, aluminates and silico-aluminates. The reference also teachesthat incorporation of pore-forming materials during production of the supports is necessary because only relatively large absorption masses are envisioned, e.g., alumina balls. Because only large absorption masses are taught, only a fixed bed reactor istaught for contacting the gas with the absorption masses, as would be appropriate for natural gas or electrolytic hydrogen decontamination, which are the disclosed uses of the process.
Ambrosini et al. in U.S. Pat. No. 4,101,631 discloses a process for selective absorption of mercury from a gas stream. This invention is limited in that it involves loading a natural or synthetic, three-dimensional, crystalline zeoliticaluminosilicate (zeolite molecular sieve) with elemental sulfur before the zeolite molecular sieve is contacted with the gas stream. Metal sulfides are not present in the zeolite molecular sieve when it is contacted with the gas stream. The use ofpellets in absorption beds is disclosed.
Chao in U.S. Pat. No. 4,474,896 discloses adsorbent compositions for the adsorption of mercury from gaseous and liquid streams. The invention is limited in that the absorbent compositions must contain polysulfide species, while sulfide speciesmay optionally also be present. Disclosed support materials are carbons, activated carbons, ion-exchange resins, diatomaceous earths, metal oxides, silicates, aluminas, aluminosilicates, with the most preferred support materials being ion-exchangeresins and crystalline aluminosilicate zeolites that undergo a high level of ion-exchange. Metal cations appropriate for ion-exchange or impregnation into the support material are the metal cations of antimony, arsenic, bismuth, cadmium, cobalt, copper,gold, indium, iron, iridium, lead, manganese, molybdenum, mercury, nickel, platinum, silver, tin, tungsten, titanium, vanadium, zinc, zirconium and mixtures thereof. Because polysulfides are a required element of the disclosed compositions, disclosedcomposition production methods include use of a sulfane, heating sulfur and a sulfide-containing support material. The only forms of adsorbent compositions disclosed were 1/16-inch pellets.
Gash et al., in "Efficient Recovery of Elemental Mercury from Hg(Il)-Contaminated Aqueous Media Using a Redox-Recyclable Ion Exchange Material," Environ. Sci. Techno., 1998, pp. 1007 1012, 32(7), American Chemical Society, discloses the use oflithium-intercalated transition metal dichalcogenides as redox-recyclable ion-exchange materials for the extraction of heavy metal ions from water. The reference also discloses a semisynthetic ion-exchange material named thiomont, which is athioalkylated montmorillonite clay. This reference is limited in that is does not disclose compositions of the type disclosed herein and the compositions that it does disclose can only be used in water treatment.
Dorhout et al., in "The Design, Synthesis, and Characterization of Redox-Recyclable Materials for Efficient Extraction of Heavy Metal Ions from Aqueous Waste Streams," in New Directions in Materials Synthesis, Winter, C. H., Ed., ACS SymposiumSeries 727, 1999, pp. 53 68, American Chemical Society, discloses the synthesis and use of lithium-intercalated transition metal disulfides as redox-recyclable materials for the extraction of heavy metals from aqueous waste streams. This reference islimited in that is does not disclose compositions of the type disclosed herein and the compositions that it does disclose can only be used in water treatment.
U.S. patent application Ser. No. 10/134,178, filed Apr. 26, 2002, discloses ion exchanged silicate substrates. The plate-like substrates support thin layers of metal sulfides between the plates. The polyvalent metals in the metal sulfidesare typically derived from one or more polyvalent metals in the transition series of the Periodic Table of the Elements. The sorbent is manufactured by conducting the ion exchange between the polyvalent metal and the ion exchange sites in the substrateunder acidic conditions. Following ion exchange, the substrates are washed to remove the acid and stabilized using a sulfide source under alkaline conditions. Although the sorbents have proven highly effective in removing mercury, whether in elementalor speciated form, the process to produce the sorbent can be expensive. The use of acidic conditions typically requires more expensive equipment than alkaline conditions and the transition from acid to alkaline conditions causes consumption of acid,thereby increasing reagent costs.
SUMMARY OF THE INVENTION
These and other needs are addressed by the various embodiments and configurations of the present invention. The present invention is generally directed to the use of polyvalent metal sulfides on substrates to remove various contaminants,particularly mercury, from contaminated fluids.
In one embodiment, a contaminant removal agent or particle is provided that includes: (a) a substrate having an ion exchange capacity of about 50 mEq/100 g or higher and pH dependent and pH independent ion exchange sites; and (b) polyvalent metalsulfides located at each of the pH dependent and pH independent ion exchange sites. The metal sulfides are preferably one or more compounds of copper and sulfur with copper sulfide (CuS) being preferred. The presence of polyvalent metal sulfides notonly on the less contaminant accessible, interlayer positioned pH independent ion exchange sites but also on the more contaminant accessible, edge, surface, and corner positioned pH dependent ion exchange sites can provide an agent having superiorkinetics for removing contaminants, particularly mercury.
The substrate preferably has an ion exchange capacity ranging from about 80 to about 150 mEq/100 g and more preferably is a silicate, such as a member of the phyllosilicate group (e.g., vermiculite or montmorillonite) or the zeolite group.
In another embodiment, a process is provided for manufacturing the agent. The process includes the step of contacting a solution including dissolved polyvalent metal ions with the substrate at a pH that is typically greater than the pHZPCto provide the ion exchanged substrate, where ZPC refers to the zero point of charge. As will be appreciated, at pH's above the pHZPC, pH dependent sites are negatively charged, below the pHZPC pH dependent sites are positively charged, and atthe pHZPC pH dependent sites are uncharged. Due to the solubility limitations imposed by pH's above the pHZPC (which are typically alkaline), the polyvalent metal is in the form of a compound that is soluble under alkaline conditions. Preferably, the polyvalent metal in the solution is complexed with ammonia. The solution is typically formed by contacting a salt of the polyvalent metal with an excess amount of ammonia.
The ion exchanged polyvalent metal (which is typically deposited as a compound or complex of the polyvalent metal and ammonia) can be instable after deposition. To stabilize the polyvalent metal, a source of sulfide ions is preferably contactedwith the ion exchanged substrate to convert the polyvalent metal into a stable compound of the polyvalent metal and sulfur. Because the polyvalent metal ions are ion exchanged for the existing metal ions, the polyvalent metal sulfides are commonlydiscontinuously distributed over the substrate surface and are not in the form of a continuous coating or layer over the substrate surface.
The present invention can have a number of advantages compared to the conventional additives. For example, the agents can provide improved and cost effective control of mercury and other toxic metal ions in fluids, including both liquids andgases. The agents of the present invention can have capacities to sorb toxic ions that greatly exceed that of current sorbents at a much lower unit cost. This is believed to be due, at least in part, to the agent's ability to sorb ions by severaldifferent mechanisms and due to the use not only of pH independent but also pH dependent sites. The increased capacity combined with an economically efficient method of deploying the polyvalent metal sulfides can offer the prospect of much more costeffective methods of toxic metal control for any facility that may require such control including, without limitation, coal-fired utilities, municipal waste incinerators, municipal water districts, small private suppliers, and point-of-use systems. Compared to conventional acidic ion exchange processes, the use of alkaline as opposed to acidic conditions during ion exchange can reduce operating and capital costs (due to the avoidance of acid consumption and the ability to use low cost processingequipment) and provide increased safety to personnel. The use of silicate-based substrates can prevent adverse effects on the quality or value of the treated fluid caused by introducing undesirable ions. The use of a silicate substrate, such asvermiculite, can provide a particle bed that has a very large surface area but creates a low back pressure. The agents can remove not only speciated mercury but also elemental mercury from mercury-contaminated gases and liquids, without costly and timeconsuming pre-oxidation or reduction. They can operate effectively on liquids having high TDS. They can be relatively pH-insensitive and can operate effectively within the pH range of groundwater without prior pH adjustment.
These and other advantages will be apparent from the disclosure of the invention(s) contained herein.
The above-described embodiments and configurations are neither complete nor exhaustive. As will be appreciated, other embodiments of the invention are possible utilizing, alone or in combination, one or more of the features set forth above ordescribed in detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of adjacent plates of a vermiculite substrate (not drawn to scale) according to an embodiment of the present invention;
FIG. 2 is a cross-sectional view of copper sulfide demonstrating intercalated mercury atoms (not drawn to scale);
FIGS. 3A and B depict the steps for manufacturing a contaminant removal agent according to an embodiment of the present invention;
FIG. 4 is a prior art plot of surface charge against pH for Mn- and Fe-oxides;
FIG. 5 is a prior art cross-sectional view of a naturally occurring vermiculite substrate (not drawn to scale);
FIG. 6 is a cross-sectional view of the substrate after ion exchange (not drawn to scale);
FIG. 7 depicts a process for treating a liquid according to an embodiment of the present invention;
FIG. 8 depicts a process for treating a gas according to an embodiment of the present invention;
FIG. 9 is a cross-sectional view of a naturally occurring bentonite substrate (not drawn to scale); and
FIG. 10 is a cross-sectional view of a naturally occurring vermiculite substrate at a pH above the pHZPC.
The present invention uses a polyvalent metal sulfide-containing contaminant removal agent to remove contaminants from fluids, particularly gases and aqueous streams. As will be appreciated, the term "sulfide" refers to a compound in which oneor more metal atoms is bonded to one or more sulfur atoms. The agent includes a suitable substrate on which is deposited/substituted the polyvalent metal sulfides by suitable techniques. Gas-phase contaminants are believed to be collected on the agentby one or more mechanisms, namely co-precipitation, adsorption, surface complex formation, ion exchange, chemisorption, and penetration, (i.e., intercalation) of the crystal lattice formed by the polyvalent metal sulfides. These mechanisms areindividually and collectively referred to as "sorption" and are discussed more fully below. Liquid-phase contaminants may also be removed by precipitation as sulfides. It is believed that the sulfides in the agent are slightly soluble in aqueoussolutions at acidic, neutral or slightly alkaline pHs (or at pH's less than about pH 8). The solubilized sulfides would cause contaminants such as mercury to precipitate as mercury sulfides.
The substrate can be any suitable substrate depending on the application. Preferably, the substrate is selected such that it is inert, does not introduce significant amounts of undesirable (toxic) contaminants, such as extraneous ions (otherthan hydroxyl and hydrogen ions), into the fluid being treated, has a high ion exchange capacity, and has a large surface area per volumetric or mass unit of material. Preferably, the ion exchange capacity is at least about 50 mEq/100 g and morepreferably ranges from about 80 to about 150 mEq/100 g or more, and the surface area is at least about 100 m2/g and more preferably ranges from about 500 to about 800 m2/g. Preferred substrates include the layered silicates, known collectivelyas phyllosilicates. These include clay minerals such as montmorillonites and micas, such as vermiculite. Phyllosilicates have a layered structure that leads to a high surface area. The substrate can also be non-layered silicates such as zeolites. Particularly preferred substrates include the minerals vermiculite and montmorillonite, with vermiculite being even more preferred.
In phyllosilicates, rings of silica tetrahedra are linked by shared oxygens to other rings in a two dimensional plane that produces a sheet-like structure. Typically, the sheets are then connected to each other by layers of cations. Thesecation layers are weakly bonded and often have water molecules and other neutral atoms or molecules trapped between the sheets. The silicon to oxygen ratio is generally 1:2.5 (or 2:5) because only one oxygen is exclusively bonded to the silicon and theother three are half shared (1.5) to other silicons. The symmetry of the members of this group is controlled chiefly by the symmetry of the rings but is usually altered to a lower symmetry by other ions and other layers; but the overlying symmetry ofthe silicate sheets will usually still be expressed in a higher pseudo-symmetry. The typical crystal habit of phyllosilicates is flat, platy, book-like and most all members display good basal cleavage. Although members tend to be soft, they areremarkably resilient. Phyllosilicates are also generally tolerant of high pressures and temperatures.
Vermiculite (i.e., hydrated laminar magnesium-aluminum-ironsilicate that resembles mica in appearance) is one preferred agent substrate, given its high ion exchange capacity, commercial availability, and low cost. Vermiculite is the name appliedto a group of magnesium aluminum iron silicate minerals, with a variable composition that may be summarized thus: (Mg, Ca)0.7(Mg, Fe3 , Al)6.0[(Al, Si)8O.sub.20](OH)4. 8H2O Flakes of raw vermiculite concentrate aremicaceous in appearance and contain interlayer water in their structure. When the flakes are heated rapidly, or treated with hydrogen peroxide, the flakes expand, or exfoliate, into accordion-like particles. The resulting lightweight material ischemically inert, fire resistant, and odorless. For these reasons vermiculite will not adversely affect the quality of water that is exposed to it.
FIG. 5 depicts the platelet structure of vermiculite. Vermiculate is a phyllo-, or layered, silicate with a generalized structure similar to that of talc. It has a central, octahedrally coordinated interlayer of iron and magnesium oxides 600lying between two silicate layers 604 of, each silicate layer having inwardly pointing sheets 606 of silica tetrahedra. In vermiculite, iron and magnesium ions 600 substitute for silicon in the tetrahedral layer and the resulting electrical imbalance isneutralized by loosely bound hydrated interlayer 608 of ions 612 of calcium, magnesium, or more rarely, sodium or potassium (or ion exchange sites). The interlayer space 608 also includes two ordered layers of water molecules 624 (depicted as beingbehind the ions 612). Referring to FIG. 10, at pH's above pHZPC, the external, exposed surfaces 1100 and edges/corners (not shown) of the vermiculite also contain ion exchange sites 1104, which are typically occupied by hydroxyl ions. The calciumand magnesium ions within the interlayer space can be replaced by other metal ions, owing to vermiculites' very high ion-exchange capacity. Vermiculite is not described in the literature as an aluminosilicate.
Montmorillonite, also known as smectite, bentonite, or Fuller's Earth, is a clay weathering product of alumino-silicate minerals. These clays typically develop in semi-arid regions from solutions with high concentrations of magnesium ions andcan be made synthetically. Montmorillonite is a crypto-crystalline aluminosilicate. As can be seen in FIG. 9, the individual plates of montmorillonite clays are constructed of a single sheet 1000 of alumina octahedra (or an octahedral sheet),sandwiched between two layers 1004 of silica tetrahedra (or tetrahedral sheets). Substitution of other atoms (Mg2 , Fe2 , or Mn2 ) for the aluminum in the octahedral layer or A13 substitution for silicon in the tetrahedral layerleads to interlayer charge imbalance, producing one excess negative charge for each substituted atom. Cations 1008, such as calcium ion, magnesium ion, and sodium ion, intercalate into the interlayer areas to balance the charge. The charge imbalance inthe interlayer region 1016 is permanent and is unaffected by the pH, the valance of the counter ions, and the electrolyte concentration of the surrounding aqueous solution. The balancing cations intercalate into the interlayer areas to balance thecharge. Water molecules 1012 are also present in the interlayer areas.
The generalized formula of montmorillonite, though variable, is:
[(1/2Ca,Na)0.7(Al,Mg,Fe)4(Si,Al)8O.sub.20(OH)47nH.sub.- 2O], where n is a whole number.
The hydrated interlayer space 1016 between the sheets is expansible, that is, the separation between the individual smectite sheets varies depending upon the interlayer cations present. Because the interlayer area is hydrated, cations within theinterlayer may easily exchange with cations in an external solution, providing that charge balance is maintained. This leads to very high cation exchange capacities in these materials that may be as high as 80 150 mEq/100 g. The availability of theinterlayer areas and the very small particle size lead to these clays having extremely large effective surface areas.
Due to a low hydrological resistance when configured as a bed and a platy (high surface area) structure, vermiculite is generally the more preferred substrate.
The polyvalent metal located on the agent can be any suitable polyvalent metal, including the transition metals. Preferred polyvalent metals include the elements in Groups 9, 10, 11, and 12 of the Periodic Table of the Elements, with metals thatform soluble complexes with ammonia being more preferred, cadmium, nickel, cobalt, silver, and copper being even more preferred, and non-toxic metals such as copper being even more preferred. The polyvalent metals are stabilized on the substrate bybeing converted into metal sulfides.
While not wishing to be bound by any theory, FIG. 1 depicts, on a microscopic level, a configuration of the agent of the present invention. The agent 100 includes a number of spaced stacked sheets 604 having surfaces 1104 and edges/corners (notshown). Between the adjacent pairs of layers 604 is a hydrated inter-layer region 104 including polyvalent metal sulfides 120 (or ion-exchange sites) and entrapped water molecules 624. Polyvalent metal sulfides 120 are also located at the ion exchangesites 1104 on the surface 1100 and edges/corners. Although not wishing to be bound by any theory, it is uncertain whether the polyvalent metal sulfides are bonded to the ion exchange sites by chemical bonds or by simple surface attachment forces, namelythose between a precipitate and the surface on which the precipitate formed, or a combination of the two, that are not considered chemical bonds. The polyvalent metal sulfides are discontinuously distributed in the inter-layer region 104 and along thesurface 1100 and edges/corners. The polyvalent metal sulfides provide a sufficient inter-plate spacing (PS (FIG. 1)) for contaminants to pass through the inter-plate region and collect on the polyvalent metal compounds. In other words, it isbelieved that the polyvalent metal sulfides "prop" open or maintain a desired inter-plate spacing distance.
The agent effectively collects both elemental and speciated mercury contaminants from the surrounding fluid. In the gas phase, mercury is a volatile metal and is preferentially attracted to sulfur atoms lining the interlayer spaces in thesubstrate.
While not wishing to be bound by any theory, the gas-phase contaminants, as noted above, are believed to be removed by one or more mechanisms, depending on the contaminate. For example, co-precipitation occurs when a contaminant forms a compoundwith a distinct chemical composition from ions in solution and the polyvalent metal amendment. The amount of contaminant that can be removed is stoichiometrically based on the amount of polyvalent metal on the agent. By way of illustration, the copperion can form an amalgam with mercury. Adsorption occurs when a contaminant is held to the surface of the agent by physical bonds. The metal ions at the surface of a sulfide have a reduced coordination number, thus they behave as Lewis acids. In thepresence of water, the surface ions first coordinate water molecules. The water molecules undergo dissociative chemisorption to form a protonated surface. The hydroxyl ions and protons at the surface of the sulfide are available for bonding or exchangewith ions in solution. Moreover, sulfur atoms can form stable compounds with mercury with the interatomic bond being van der Waal-type forces. Surface complex formation is characterized by sorption followed by bidentate complex formation. Compared toco-precipitation, surface complex formation is not limited by stoichiometry in the amount of contaminant that can be removed. Ion exchange involves the exchange of ions between a solid and a solution. Finally, penetration of the crystal lattice refersto the insertion of metal ions into the crystal lattice structure of the polyvalent metal sulfides by occlusion.
The intercalation mechanism is depicted by FIG. 2, where the polyvalent metal(s) (not shown), which in the figure is copper, is located in the center of the sulfur tetrahedrons 300. The tetrahedrons 300 are linked at their bases 304 to form thintetragonal sheets 308. Some of the polyvalent metal(s) are combined with three sulfur ions in flat triangular groups 312 similar to the triangular groups of carbonates. The triangular groups 312 lie in a plane between adjacent tetragonal sheets 308. One or more of the tetragonal sheets are located on the adjacent plates interlayer surfaces 130 of the substrate (see FIG. 1). The rear surfaces 316 and 320 of the outermost copper sulfide tetragonal sheets 308 are each bonded to the opposing interlayersurfaces 130 of the plates (FIG. 1) in the substrate 100 in the interlayer area 104 (FIG. 1). In the intersheet area 324 between the outermost tetragonal sheets 308, mercury atoms 328 are intercalated. Typically, the average ratio of copper atoms tosulfur atoms is around 1:1, so that the copper sulfide is in the form of copper sulfide or CuS. As can be seen from FIGS. 1 and 2, phyllosilicates and copper sulfide have similar sheet- or plate-like structures.
The process to form the agent of the present invention will now be described with reference to FIGS. 2 6. Although any suitable technique for forming the agent may be employed, a preferred process chemically deposits and/or substitutes thepolyvalent metal sulfides onto or into the substrate. For economic efficiency, the sulfides are deposited onto the substrate in such a manner as to ensure maximal exposure of the sulfide to the ions in the fluid while substantially minimizing the amountof the more expensive amendment required.
Referring to FIG. 1, it can be seen that polyvalent metal sulfides are located not only in the interlayer ion exchange sites but also in the ion exchange sites 1104 on the surface 1100 and edges/corners of the layers 604. While the ion exchangesites in the interlayer region 104 are pH independent, the ion exchange sites 1104 on the more exposed (and more contaminant accessible) surface 1100 and edges/corners are pH dependent. As discussed below, the ion exchange capacity of the pH dependentsites depends on the surface charge on the substrate 100 while the ion exchange capacity of the pH independent sites is independent of the surface charge. The availability of ion exchanged sites on the edges and corners in addition to the interlayerregion can enhance substantially the contaminant removal efficiency relative to existing mercury sorbents, such as those of copending U.S. patent application Ser. No. 10/134,178 above in which ion exchange is performed only in the interlayer region dueto the use of acid and not alkaline conditions during ion exchange.
Referring now to FIG. 3A, a raw substrate 400 is comminuted in step 404 by suitable techniques, such as by wet or dry crushing, wet or dry grinding, and the like, to form a slurried comminuted substrate 408. The slurried comminuted substrate 408preferably has a P90 size of no more than about 10 microns.
In step 412, solid/liquid separation is performed to separate the comminuted substrate 416 from the water 420. Any suitable solid/liquid separation technique may be employed including filtering or centrifuging. The water 420 may be recycled tothe comminution step 404.
In step 424, ammonia is added to a metal salt solution 428 and the mixture blended in step 432 to form a metal ammonia solution 436. The metal salt may be in any form, such as a chloride, sulfate, nitrate, and/or hydroxide. The concentration ofthe polyvalent metal in the metal salt in the metal solution 428 preferably ranges from about 2 to about 15 wt %, and the pH of the solution 428 from about pH 1 to about pH 2. Sufficient ammonia is added to the solution 428 to convert at least most ofthe polyvalent metal into a polyvalent metal-ammonia complex. As used herein, "polyvalent metal ammonia complex" includes any complex or compounds between the polyvalent metal cation and the ammonia ion, including without limitation the tetramminecopper complex and cuprammonium complex. When copper is the polyvalent metal, copper is initially precipitated as a copper hydroxide, and the solution turns opaque. Continued addition of ammonia redissolves the copper hydroxide and causes the solutionto turn dark blue. Preferably, at least most, more preferably at least about 95% of the polyvalent metal in the metal ammonia solution 436 is in the form of a dissolved polyvalent metal-ammonia complex (such as tetrammine copper, or cuprammoniumcomplexes). Typically, the concentration of the polyvalent metal-ammonia complex in the metal ammonia solution 436 ranges from about 1 to about 10 wt. %. The pH of the metal ammonia solution typically is at least about pH 7, and even more typically atleast about pH 9, to about pH 10 to about pH 12.
In step 440, the comminuted substrate 416 is mixed and agitated with the metal ammonia solution 436 for a time sufficient to replace the existing metal cations 612 (FIG. 5) in the native substrate with desired polyvalent metal cations to form anion exchanged substrate-containing slurry 444. Typically, sufficient metal ammonia solution 436 is added to produce a slurry in which the volumetric solid/liquid ratio is at least about 5%, more typically from about 10 to about 50%, and even moretypically from about 10 to about 30%. The mixing and agitating can be done by any suitable technique, such as stirring, tumbling or pumping.
The concentration of the dissolved polyvalent metal-containing ions/compounds is super-equilibric relative to the concentration of the exchanged metal cations 612 in the salt solution. In this manner, the metal cations 612 are driven intosolution and the polyvalent metal cations out of solution (to replace the metal cations 612) in an attempt to attain an equilibrium concentration of the metal cations 612 and polyvalent metal cations in the metal ammonia solution 436. As noted above,polyvalent metal ammonia complexes replace native cations at the interlayer (pH independent) ion exchange sites and protons at the surface (pH dependent) ion exchange sites. To realize substantially complete ion replacement of the native metal cations612, the pH of the surrounding metal ammonia solution 436 is maintained at a level necessary to realize a substantially complete replacement of the native metal cations 612. Preferably, the duration of the mixing and agitating step 440 typically rangesfrom 1 to about 24 hours and more typically from about 2 to about 8 hours. Typically, at least about 90% of the native metal cations 612 are replaced by polyvalent metal cations.
The pH of the metal ammonia solution 436 and the slurried comminuted substrate 444 during the mixing step 440 can be important. In clay/aqueous systems, the potential of the clay surface is determined by the activity of ions that react with themineral surface. The zero point of charge (ZPC) at the clay surface is the point at which the total charge from the cations and anions adsorbed onto the surface is zero. This is illustrated graphically by FIG. 4, which shows the relationship betweensurface charge and pH for manganese oxide and iron oxide. A similar graphical relationship exists for clays. The principal potential determining ions are protons and hydroxyl ions. The pH that corresponds to the ZPC is referred to as the pHZPC orthe isoelectric point. When the pH of the solution in contact with the clay is below the pHZPC, basal planes and edges and corners of the tetrahedral layers carry positive charges and exhibit an anion exchange capacity. At the pHZPC, thesolid exhibits no ion exchange capacity and at a pH above the pHZPC, the basal planes of the silica tetrahedra are negatively charged and exhibit a cation exchange capacity.
Accordingly, clays, such as montmorillonite, exhibit two forms of exchange one of which is pH independent and one that is pH dependent. The pHZPC of various substrates depends of course on the substrate. For example, the pHZPC formontmorillonite is from about pH 2 to about pH 3.
The pH of the metal ammonia solution 436 immediately before the mixing step 440 and of the slurried comminuted substrate during the mixing step 440 is preferably above the pHZPC more preferably at least about pH 7, even more preferably atleast about pH 9, and even more preferably ranges from about pH 10 to about pH 12. At higher pH's, the ion exchange capacity is typically increased by at least about 80 to about 120% relative to ion exchange performed at pH's below the pHZPC.
FIG. 6 depicts the ion exchanged substrate 448. The substrate 448 comprises copper ions (Cu.sup. ) and tetrammine copper complex ions Cu (NH3)4.sup. ) exchanged for the cations 612 (FIG. 5) in the interlayer region 104 and tetramminecopper complex ions exchanged for the hydrogen ions (or protons) at ion exchange sites 1104. As will be appreciated, other compounds between copper and ammonia may be present at the ion exchange sites, such as diammine.
With the exception of the alkali metals, most metal ions precipitate from alkaline solutions as the hydroxides and oxides. Simple salts of the metal ions cannot therefore generally be used as a source of the exchangeable ions in alkalineconditions. However, certain metals form complex ions, which are soluble in alkaline solutions. Copper is an attractive alternative for this application as it forms a number of different complexes with ammonia and other soluble compounds such aspyridine. These complexes include Cu(NH3), Cu(NH3)2, Cu(NH3)3, and Cu(NH3)4. Copper is not a RCRA metal and therefore does not pose a toxicity issue. Other metals also form ammonia complexes, but in certainapplications they are too toxic and/or expensive or the sulfides of the metals form three-dimensional structures, with little potential capacity for mercury. While not wishing to be bound by any theory, it is believed, as shown in FIG. 2, that coppersulfide has a two-dimensional layered structure with sheets being bonded by van der Waals forces, and the weak intersheet bonds permit mercury to intercalate into the intersheet spaces where the mercury is held by the sulfur and metal ions lining theopening.
The resultant ion exchanged substrate-containing slurry 444 (which includes the ion exchanged substrates 448 and the metal ammonia solution 436) are subjected in step 452 to liquid/solid separation, such as by pressure filtration, screening,settling, flotation, or centrifuging, to separate the ion exchanged substrates 448 from the ion exchanged solution 456 and the ion exchanged substrate 448. The recovered ion exchanged substrate 448 is rinsed to remove the excess ion exchanged solution456.
The recovered metal ammonia solution contains exchanged native cations, such as those set forth above, and substantial amounts of the polyvalent metal and ammonia. In step 460, at least most of the polyvalent metal is recovered by suitabletechniques, such as electrolysis and precipitation of the polyvalent metal (such as as a hydroxide or sulfide) to produce the recovered metal 464. The polyvalent metal depleted solution 468 in step 470 is subjected to ammonia recovery by suitabletechniques. An example is to add a source of hydroxide ions to the solution 468 which precipitates the remaining dissolved polyvalent metal, regenerates the ammonia ion, and generates ammonia gas. The ammonia gas can be captured and condensed forreuse. Distillation of the ammonia may be used to enhance recovery. The recovered metal 464 is recombined and regenerated with fresh metal salt solution to form the metal salt solution 428 and recovered ammonia 472 regenerated with fresh ammonia andadded to the metal salt solution 428 as noted above. The waste solution 474 may be discarded.
The ion exchanged substrates, in step 475, are reslurried and in step 476 contacted with a source of sulfide ions, such as sulfide solution 480, to yield the stabilized ion exchanged substrate-containing slurry 478 and subjected to furthermixing/agitating by suitable techniques for a sufficient period of time for at least most, and typically about 95%, of the polyvalent metal cations on the substrates to be converted into sulfides. Sulfide precipitation will release the ammonia ionspresent in the polyvalent metal ammonia complexes back into solution. As will be appreciated, the polyvalent metals are volatile on the substrate unless stabilized by a suitable technique. The preferred technique is to convert the polyvalent metal intoa sulfide, though other techniques may be employed. The source of sulfide ions may be any suitable compound, such as an alkali metal sulfide or polysulfide solution, an alkaline earth metal sulfide or polysulfide solution, a thiocarbonate solution,hydrogen sulfide gas, ammonium sulfide, and mixtures thereof.
The sulfide solution 480 typically contains a superstoichiometric amount of sulfide ions relative to the amount of polyvalent metal ions and has a pH of at least about pH 8 and more typically ranging from about pH 10 to about pH 12. Typically,the sulfide solution 480 contains at least about 2 wt. % and more typically from about 5 to about 20 wt. % of sulfide ion. A precipitate of the polyvalent metal ions forms immediately from the excess polyvalent metal ammonium ions carried over in thesolution that is carried over from the solid/liquid separation step 452. Metal ions that have been exchanged into the lattice of the substrate also react to form the sulfide and become immobilized in place within the substrate such that, during fluidtreatment, the metal ions do not enter solution. The agent of FIG. 1 results from this step when vermiculite is the substrate.
While not wishing to be bound by any theory, it is believed that the alkali or alkaline earth metals in the sulfide solution 480 are attracted by the substrate to balance the charge imbalance caused by the formation of copper sulfide. As will beappreciated, copper sulfide has a zero charge. The substrate has a negative charge. Accordingly when copper sulfide forms, the substrate will have a net negative charge where the copper sulfide is deposited. The alkali or alkaline earth metals have apositive charge and are believed to physically bond to the substrate to cause a zero net charge.
As will be appreciated, steps 475 and 476 can be performed simultaneously. The ion exchanged substrate can be slurried using the sulfide solution alone or in conjunction with an aqueous solution. The volumetric ratio of the sulfide solution 480to the ion exchanged substrate 448 is typically from about 5:1 to about 10:1 to yield a solids content of the stabilized ion exchanged substrate-containing slurry 478 ranging from about 10 vol. % to about 20 vol. %. The pH of the sulfide solution duringthe mixing step preferably ranges from about pH 10 to about pH 12.
In step 482, the stabilized ion exchanged substrate 484 is separated from the residual sulfide solution 486 by liquid/solid separation techniques, such as those set forth above in connection with steps 412 and 452. The stabilized substrate 484is dried in step 490 using a suitable dryer, such as a hollow flight dryer, porcupine dryer, spray dryer, and the like.
In step 494, the dried stabilized ion exchanged substrate is disaggregated to form the agent 498.
The recovered sulfide-containing filtrate 486 contains not only the sulfide ion source but also ammonia ions. The ammonia ions were typically part of a complex with the polyvalent metal. The recovered sulfide-containing filtrate 486 can becombined with the depleted ammonia solution 468 to cause polyvalent metal sulfide precipitation followed by ammonia recovery or independently subjected to extractive distillation to recover the ammonia.
The final product or agent 498 can be substantially different in color compared to the original substrate. For vermiculite as the substrate, the color is commonly substantially different but the vermiculite retains the luster of the original(native) material. This indicates that the polyvalent metal sulfides have been introduced into the structure of the vermiculite rather than being merely a surface coating.
Referring now to FIG. 7, the process for treating a fluid, such as water, is described. In step 800, the fluid 804 (which typically is a liquid having a pH ranging from about pH 5 to about pH 9) is contacted with the agent 498 in any suitablemanner. Preferably, the fluid is passed through a fluidized or fixed bed of the agent particles. The particle size of the agent can be important in optimizing contaminant removal from liquids. For liquid treatment, the average particle size of theagent particles 498 is larger than about 60 mesh. A preferable range is from about 30 mesh to about 5 mesh. In step 612, the treated fluid 816 is separated from the contaminant laden agent 820 (or removed from the bed). The residence time of the fluid804 in the contacting step 800 is typically at least a few tens of seconds, with at least about 120 seconds being preferred. After fluid treatment, the agent particles 808 eventually become laden with the contaminant 832 so as to be less effective incontaminant removal. The contaminant laden agent 820 can be stabilized in step 824 by known techniques, if needed, and disposed of. Alternatively, the agent can be regenerated in step 828 chemically or thermally by known techniques to remove thecontaminants 832 and reused to treat further fluid.
FIG. 8 depicts a process for treating a gas, particularly a mercury containing flue gas generated by the combustion of coal. The coal is combusted in step 900 to produce a flue gas 904. The flue gas 904 typically includes particulates, such asfly ash. The agent, which behaves as a sorbent, may be introduced into the flue gas in step 908 by suitable techniques, such as by injection. The preferred size of the agent particles is in the range of about 2 to about 10 microns to ensure adequategas contact and distribution in the gas stream. In step 912, the entrained particulates, (which would include the agent particles) are removed by suitable techniques, such as by an electrostatic precipitator or baghouse, to produce recovered fly ash 916and an off-gas. The off-gas may be contacted with the agent in step 920, such as noted above in step 908 or by passing the gas through a fluidized or packed bed of the agent, to produce an environmentally acceptable off-gas 924.
The amount of contaminant(s) removed from the fluid can be high. Preferably, at least about 90% of the contaminants are removed to provide a final contaminant concentration of no more than about 10% of the initial untreated concentration. Influe gas applications, the starting concentration of mercury in the gas stream is typically in the range of 2 to about 20 micrograms/m3. Assuming that at least about 90% of the mercury is sorbed by the agent, the residual mercury concentration inthe gas stream typically is 0.2 to 2 micrograms/m3. Loadings of up to 12 milligrams of mercury by weight of the amended vermiculite have been realized.
This Example describes preparation of several polyvalent metal sulfide-substituted sorbents of the present invention, using various amounts of cuprammonium ion for substitution.
All steps in all Examples (unless otherwise noted) were carried out at room temperature. All reagents are obtainable from Sigma Chemical, St. Louis, Mo.) except as noted. To a beaker, approximately 20 milliliters (mL) of copper chloride, togive a final concentration of 2%, 5%, or 10% (w/v) of copper in 100 mL, was added. Following addition of copper chloride, enough ammonium hydroxide was added to dissolve the copper chloride. Distilled deionized water was then added to bring thesolution to 100 mL total. See Table 1 for further experimental details. To the prepared cuprammonium reagent, 10 g of vermiculite Palabora #4 (obtainable from Palabora, Inc. Palabora, South Africa), ground or milled to 90% less than 10 micrometers,were weighed out and placed in each beaker to form a slurry. All substrates are pretreated before use by exfoliation (either by hydrogen peroxide treatment or heat treatment) and ground or comminuted to approximately 10 microns. The slurry was thenrotated at approximately 50 rpm overnight. After incubation, the reaction was centrifuged in order to separate the liquid and the solid, and the liquid was removed for metal recovery. After the overnight reaction, the polyvalent metal is stabilized toyield stabilized ion-exchange substrate by resuspending the solid using a 10% aqueous solution of sulfide to form a slurry. In this Example, either sodium sulfide or CASCADE (calcium polysulfide, available from BSP, Inc., Fresno, Ca) was added,approximately 100 ml. The slurry was then centrifuged to separate the liquid and the solid. The solid was rinsed once with 100 mL distilled deionized water, and recentrifuged to remove liquid. The solid then consisted of a stabilized ion exchangesubstrate. The stabilized ion exchange substrates were then dried at 40° C. overnight.
TABLE-US-00001 TABLE 1 Preparation of cuprammonium solution at 2%, 5%, and 10% copper Formulation % Copper in Weight (g) CuCl Moles ml Number solution added to solution copper NH4OH added 1 2 4.23 0.031 10.5 1A 2 4.23 0.031 10.5 2 5 10.60.0787 40 2A 5 10.6 0.0787 40 3 10 21.15 0.1574 80 3A 10 21.15 0.1574 80
This Example describes preparation of several polyvalent metal sulfide-substituted sorbents of the present invention, using various amounts of cuprammonium ion for substitution.
All steps described in Example 1 were carried out in this Example, with the exception being in the sulfide addition step. In this Example, either sodium sulfide or CASCADE (calcium polysulfide, available from BSP, Inc., Fresno, Ca) was addeduntil the pH was above 8. The slurry was processed to completion as described in Example 1.
TABLE-US-00002 TABLE 2 Preparation of cuprammonium solution at 2%, 5%, and 10% copper Formulation % Copper in Weight (g) CuCl Moles ml Number solution added to solution copper NH4OH added 1 2 4.23 0.031 10.5 1A 2 4.23 0.031 10.5 2 5 10.60.0787 40 2A 5 10.6 0.0787 40 3 10 21.15 0.1574 80 3A 10 21.15 0.1574 80
This Example describes preparation of several polyvalent metal sulfide-substituted sorbents of the present invention, using various amounts of cuprammonium ion for substitution.
All steps described in Example 1 were carried out in this Example, with the exception being in the sulfide addition step. In this Example, either sodium sulfide or CASCADE (calcium polysulfide, available from BSP, Inc., Fresno, Ca) was added asfollows. When the amount of sulfide added was 126 mL, a final pH of 9.44 was recorded. When the amount of sulfide added was 132 mL, a final pH of 10.2 was recorded. The slurry was processed to completion as described in Example 1.
TABLE-US-00003 TABLE 3 Preparation of cuprammonium solution at 2%, 5%, and 10% copper Formulation % Copper in Weight (g) CuCl Moles ml Number solution added to solution copper NH4OH added 1 2 4.23 0.031 10.5 1A 2 4.23 0.031 10.5 2 5 10.60.0787 40 2A 5 10.6 0.0787 40 3 10 21.15 0.1574 80 3A 10 21.15 0.1574 80
This Example describes a mercury sorption test to determine the mercury capacity of a stabilized ion exchange substrate of the present invention.
According to sources, mercury capacity of a sorbent as determined in a packed bed configuration is a reliable indication of the performance of the sorbent when dispersed in a flue gas stream (Meserole et. al., 1999). A system to determinemercury capacity of a sorbent in a packed bed may be constructed as follows. The system consisted of a laboratory furnace, a system to supply the test gases, a mercury analyzer, and a data acquisition system. The sorbent material was placed in a 1/2''diameter by 10'' long stainless steel tube and connected into system plumbing. Piping held the sorbent tube inside an electric tube furnace. The furnace was used to control the temperature of the sorbent chamber during the sorption and desorptionprocesses. The test gas mixture was a blend of nitrogen, oxygen, carbon dioxide, water vapor, sulfur dioxide, and nitrogen oxides. Several mass flow controllers were used to meter individual gases together. High-pressure gas cylinders supplied allgases except nitrogen, which was provided by a nitrogen membrane system. Oxygen content in the nitrogen stream was roughly 8% by volume. Finally, the test gas was humidified by passing a stream of nitrogen through a water chamber, with the humiditylevel determined by the temperature of the water.
Mercury permeation tubes from VICI Metronics (Poulsbo, Wash.) provided the mercury source for the sorption tests. The permeation tubes are made of 1/4'' silicone tubing with liquid elemental mercury inside. Caps are used on the ends of thetubing to contain the mercury. The diffusion rate of mercury through the wall of the tube is a function of the geometry of the tube and the temperature at which the perm tube is stored. A single perm tube was placed in a 1'' diameter stainless steeltube and maintained at a temperature of 104° F. inside a laboratory oven. A stream of dry nitrogen gas flowed through the stainless steel tube to transport the mercury-containing gas to the test gas manifold. There, the mercury mixed with theother gases to create the sorption test gas. The mercury concentration in the test gas is determined by the mercury emission rate from the perm tube divided by the total gas flow rate. For this project, the mercury concentration varied between 50 to 70μg/m3, depending on the test.
Sorbents were prepared as described in Examples 1 3 with the exception that montmorillonite was substituted for vermiculite for some of the test sorbents. In this Example, stabilized ion exchanged agents using either bentonite (montmorillanite)or vermiculite as the substrate were prepared as described in Examples 1 3. For samples #7 and #8 in Table 5, bentonite was obtained from the Lovell mine, Wyoming. Substrates were substituted at the 10% copper level with cuprammonium, then treated witheither calcium polysulfide or sodium sulfide as described in Examples 1 3.
All sorbent tests were conducted with either a 0.1-gram or 0.5-gram sample of sorbent dispersed in 20 grams of quartz sand ( 50, -70 mesh) and placed in the sorbent tube with glass wool plugs above and below the sorbent bed to hold it inposition. The sorbent tube was connected into the sorption test chamber plumbing and heated to 280° F. Hot nitrogen gas flowed through the sorbent test chamber while the equipment was heated to the sorption temperature. Once the test fixturewas up to temperature, the other gases (carbon dioxide, sulfur dioxide and nitric oxide/nitrogen dioxide) were added. The composition of the test gas was chosen to simulate a flue gas burning an eastern bituminous coal. Table 4 lists the testconditions for the sorbent tests.
TABLE-US-00004 TABLE 4 Summary of Sorbent Test Conditions Sorption Test Gas Parameter Nominal Condition Sorption Temperature 290° F. Sorption Pressure 12 psia Gas Flow Rate 944 sccm Test Gas Constituents Nominal Concentration SulfurDioxide 1200 ppm Nitric Oxide/Nitrogen Dioxide 400 ppm Carbon Dioxide 12% Oxygen 5% Water 7% Nitrogen Balance Elemental Mercury 50 70 microgram/sm3
Once loaded into the test fixture, the sorbents were exposed to the test gas until significant mercury breakthrough (>50%) was detected. At that time, the sorption process was halted. At the end of the sorption cycle, the acid gases andmercury were discontinued so that only nitrogen was flowing through the sorbent chamber while the chamber was cooled to ambient temperatures. The sorbent/sand mixture was removed from the test fixture and digested with an aqua-regia solution. Briefly,the sorbent/sand mixture was placed in a beaker, and 10 mL of 12N HCl was added. The mixture was heated on a hot plate but not to boiling. After ten minutes, 10 mL of 16 N nitric acid was added and allowed to sit overnight, uncovered, on a hot plate(but not to boiling). The mixture is then allowed to cool and diluted to 100 mL with distilled, deionized water. The leachate was then analyzed for total mercury by atomic absorption using a Perkin-Elmer CVAA according to manufacturer's instructions. Table 5 shows results of these tests, expressed as ug Hg per gram agent (stabilized ion exchange sorbent containing agent).
TABLE-US-00005 TABLE 5 Mercury sorption capacity of several stabilized ion exchange agents of the present invention. Prepared as described in Percent Capacity test Example substrate copper sulfide source ug/g 1 1 Vermiculite- 10 Cascade 640Palabora 2 2 Vermiculite- 10 Cascade 1128 Palabora 3 3 Vermiculite- 10 Cascade 12500 Palabora 4 2 Vermiculite- 10 Cascade 10000 Palabora 5 1 Vermiculite- 10 sodium sulfide 152 Palabora 6 2 Vermiculite- 10 sodium sulfide 176 Palabora 7 1 Bentonite- 10sodium sulfide 26.4 Lovell 8 1 Bentonite- 10 Cascade 642 Lovell
The results from Table 5 show that all sorbents contain ion exchange sites capable of sorbing mercury. Variability between samples may be due to the fact that sorbents prepared as described in Example 1 may not have been completely stabilizeddue to the fact that sulfide was not added in sufficient quantity to attain pH 8.
A number of variations and modifications of the invention can be used. It would be possible to provide for some features of the invention without providing others. In one alternative embodiment, ion exchange is performed under acidic conditionsbut at a pH above the pHZPC. Operating under such conditions can effect ion exchange at both pH dependent and independent sites. As will be appreciated, metal salts can be used under such conditions to effect ion exchange.
The present invention, in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, subcombinations, and subsets thereof. Those of skillin the art will understand how to make and use the present invention after understanding the present disclosure. The present invention, in various embodiments, includes providing devices and processes in the absence of items not depicted and/ordescribed herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.
The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. In the foregoing Detailed Description forexample, various features of the invention are grouped together in one or more embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requiresmore features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into thisDetailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.
Moreover though the description of the invention has included description of one or more embodiments and certain variations and modifications are within the scope of the invention, e.g., as may be within the skill and knowledge of those in theart, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to thoseclaimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.
* * * * *
Field of SearchMetal or metal containing compound sorbed
SOLID SORBENT APPARATUS
Plural diverse separating means
At least one a dispersed or impregnated solid sorbent bed
Plural housings or casings for separating components
MODIFYING OR REMOVING COMPONENT OF NORMALLY GASEOUS MIXTURE
With coating, impregnant, or bonding agent